Nitroallyl alcohol esters and method of making same



United States Patent 3,000,934 NITROALLYL ALCOHOL ESTERS AND METHOD OF MAKING SAME Karl Klager, Monrovia, Oalih, assignor to Aerojet-General Corporation, Azusa, Cali, a corporation of Ohio No Drawing. Filed July 15, 1957, Ser. No. 672,538 11 Claims. (Cl. 260-488) This invention relates to new compositions of matter and in particular to esters of nitroallyl alcohols having the general formula:

N 0: O 0H,:d-0Hr-0-ii-R wherein R is a lower alkyl radical.

These compositions find valuable use as components of propellant mixtures, fuels, and explosives due to their favorable oxygen balance. In addition they react with compounds containing labile hydrogen, such as dinitroethane, to produce highly nitrated compounds, such as 2,2,4,6,6-pentanitroheptane, as more fully disclosed in my copending U .S. patent application Serial No. 337,211, filed February 16, 1953.

The highly nitrated compounds of the copending patent application are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in U.S. Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives in a device such as that disclosed in US. Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulmiuate.

This application is a continuation-inpart of my copending US. patent application Serial No. 445,885, filed July 26, 1954, now abandoned, which was a continuationin-part of my US. patent application Serial No. 220,366, filed April 10, 1951, now abandoned' The esters of this invention are prepared by the simple distillation, at reduced pressures, of a diester of 2-nitro- 1,3-pr opanediol in accordance with the general reaction scheme set forth below:

wherein R is a lower alkyl radical.

The diesters used as starting materials in the practice of this invention are prepared by simply condensing an acid halide or anhydride with 2-nitro-1,3-propanediol. It is usually convenient to simply evaporate the residual volatile material from the reaction mass and then distill to eifect the conversion to the desired monoester. The distillation conversion does not require the presence of any special catalysts nor does it require any involved manipulations. The following example is presented to more clearly illustrate the invention.

EXAMPLE I The preparation of Z-m'troallyl acetate Nine gm. 2-nitro-1,3-propanediol, 17.3 gm. acetylchloride and 25 ml. chloroform is refluxed for three hours on a steambath. After evaporation of all volatile material the residue is distilled at 100 mm. and 130-l40 C. airbath temperature. After redistillation of the yellow oil 3,000,934 Patented Sept. 19, 1961 obtained, a nearly colorless liquid is collected at 90 C. airbath temperature at 4 mm., n 1.4519.

Analysis.-Calcd. for C H- O N: percent C, 41.38; percent H, 4.86; percent N, 9.65. Found: percent C, 41.35; 5 percent H, 5.17; percent N, 9.87.

Reaction temperature is not critical in the condensation of the acid halide, or anhydride, with 2-nitro-l,3- propanediol to form the diester of 2-nitro-l,3-propanediol, which is subsequently converted to the monoester by distillation at reduced pressure as taught herein. The only effect of temperature variation on the condensation reaction is a corresponding increase or decrease in reaction rate.

It is readily apparent that by simply substituting the higher homologues of acetylchloride such as propionyl chloride, n-butyryl chloride, or the corresponding anhydrides, that the valuable higher homologues of 2-nitroallyl acetate can be readily obtained by following the same simple procedure outlined above. For example propionyl chloride condenses with 2-nitro-1,3-propanediol to yield the di-propionic acid ester of 2-nitro-l,3-propanediol, which upon distillation at reduced pressure is converted to nitroallyl propionate. Also, n-bu-tyric anhydride condenses with 2-nitro-1,3-propanediol to give the di-butyric acid ester of 2-nitro-1,3-propanediol which is distilled, as taught herein, to convert it to nitroallyl butyrate.

It will also be seen that in place of eflecting the conversion by distillation from the reaction mass of the starting material, that the starting material itself may be separated and purified prior to distillation.

I claim:

1. As compositions of matter, the esters of nitroallyl alcohol having the formula:

N02 cHFhcH,-0o-R wherein R is a lower alkyl radical.

2. As a composition of matter, nitroallyl acetate having the structural formula:

N0: H CHFGHzOCCI-Is 3. As a composition of matter, nitroallyl propionate having the structural formula:

-4. As a composition of matter, nitroallyl butyrate having the structural formula:

5. The method of preparing an ester of nitroallyl alcohol having the formula:

NO: oHi=d-cH-0(":R which comprises distilling a diester of Z-nitropropanediol having the formula:

NO: R- ho-cHi-t zuomo-i zn wherein R is a lower alkyl radical, at reduced pressures.

6. The method of preparing nitroallyl acetate which comprises distilling, at reduced pressures, the di-acetic acid ester of 2-nitro-1,3-propanediol.

7. The method of preparing nitroallyl acetate which comprises refluxing 2-nitro-l,3-propanediol with acetylchloride and subsequently distilling the resultant diester, at reduced pressures, to eflect a conversion to the desired nitroallyl acetate.

8. The method of preparing nitroallyl propionate which 3 comprises distilling, at reduced pressures, the di-propionic acid ester of 2-nitro-1,3-propanediol.

9. The method of preparing nitroallyl propionate which comprises refluxing 2-nitro-1,3-propanediol with propionyl chloride and subsequently distilling the resultant diester, at reduced pressures, to effect a conversion to the desired nitroallyl propionate.

10. The method of preparing nitroallyl butyrate which 4 comprises distilling, at reduced pressures, the di-n-butyric acid ester of 2-nitro-1,3-prcpanediol.

11. The method of preparing nitroallyl butyrate which comprises refluxing Z-nitro-lfi-propanediol with n-butyric anhydride and subsequently distilling the resultant diester, at reduced pressures, to effect a conversion to the desired nitroallyl butyrate.

No references cited. 

5. THE METHOD OF PREPARING AN ESTER OF NITROALLYL ALCOHOL HAVING THE FORMULA: 